Recovery of thorium and rare earths from metallurgical sludges



April 12, 1960 .1. P. FLYNN 2,932,555

RECOVERY OF THORIUM AND RARE EARTHS FROM METALLURGICAL sLuDGEs Filed oct. 4, 1957 Mayr; @.s/'um S/uoge L each 5 Tanks 2 Sheets-Sheet 1 INVENTOR. F/Uano/e fg: dames H F75/nn April 12, 1960 J. P. FLYNN 2,932,555

RECOVERY 0E THOEIUM AND RARE EAETHs FROM METALLURGICAL SLUDGES Make-up Malr'l'/ I' ii Y l f 12 ,qc/O/ Read or Was/1 Jo//a/.sj i6 L /qu/'a S epara//on Filed Oct. 4, 1957' 2 Sheets-Sheet 2 Thor/'um or' Rare far/h Mefa/ Oxide F, 2 INVENTOR. Z James f? F/ynn Y BY HTTORNEYS quired to precipitate the lluoride of the alloying element. Suicient make-up oxide, or hydroxide, of the alloying element must therefore be added to allow dissolution of this excess magnesium fluoride which will otherwise remain to contaminate the recovered product. A 90 to 95 percent pure product containing, as the main impurity, magnesium iluoride, is readily obtained in accordance with the invention upon prolonged acid digestion of stoichiometric proportions of the oxide of the alloying element and magnesium lluoridef The presence of a small amount of magnesium fluoride does not adversely affect alloying eiiciency and therefore does not prevent this product from being quite satisfactory for the preparation of alloys. However this productl should not be considered limited to this use. l f

If the above acid digestion is continued for a sutiliently longer period to dissolve the remaining more refractory magnesium lluoride, the lluoride of the alloying I element is obtained in good purity. This procedure may be further modified in order to obtain a substantially pure fluoride product. Make-up oxide of the alloying element in excess of stoichiometric proportions is added 'to the acid digestion mixture ito promote dissolution of all the magnesium fluoride. After dissolution of the magnesium iiuoride is complete, as` determined by chemical analysis, the excess of the alloying element, now present in solution','is precipitated by the addition of a requisite quantity of hydrofluoric acid.

In carrying out the invention, reference being had to Figure l, magnesium sludge 1 is leached 2 with water 3 'to dissolve readily soluble salts and break down the mass into a slurry 4. A filtration or decantation step 5 serves to separate the undissolved solids 6 from soluble salts in solution 7.

Water leaching is generally completed in about two days. Agitation of the mass speeds up the leaching process. Acid leaching of vthe original sludge would serve to break down the mass more quickly than water leaching but would have several disadvantages if carried out as the lirst stage of the process. Part of the acid would be consumed by reaction with free 'metals in the sludge. A substantial part of the metallic alloying element present would be leached with the acid, enter solution, and be lost in the leach liquor.

To eliminate such problems from the acid digestion step the water leached sludge is dried andv calcined 8. Temperatures in the range 600800 C. are effective without at the same time causing decomposition of magnesium fluoride. The calcined material'9 then consists of magnesium fluoride, magnesium oxide, the oxide of the alloying element, and salts'not removed by water leaching, all reduced to a friable powder which is preferably blended and then sampled for chemical analysis. Results of the analysis are used to calculate the requisite amount of make-up material 10 (generally the oxide of the alloying element) to add during acid digestion in the reactor 11. Acid digestion is'carried out in nitric acid, hydrochloric acid or hydrobromic acid 12 added in such amount that the acid concentration in the solution upon completion of the digestion is about 0.5 molar, although other concentrations may be used.

The quantity of acid required for the digestion process is the sum of the acid required to react with the basic components of the saline sludge, and with the make-up oxide, plus the amount necessary to give the desired final acidity. Optimum results are obtained with a final hydrogen ion concentration between 0.5 and 2 molar. The digestion will proceed at acid concentrations between 0.1 and 6 molar, but above 6 molar acidity the process is very slow.

p The volume to which the acid medium is diluted must be such that the magnesium salt of that same acid will not precipitate out of solution on cooling. In practice, the use of one liter of dilute acid per 250 grams of leached, calcined saline sludge has been satisfactory.

Nitric acid acts much more rapidly on thorium com pounds than hydrochloric acid or hydrobromic acid. Hydrochloric acid and hydrobrornic acid though slower, are adequate for the conversion of rare earths. Acid digestion is accomplished at a gentle reflux temperature to 112 C.) in a period of 10 to 90 hours during which time magnesium fluoride gradually dissolves and the fluoride of the alloying element precipitates. At this point, addition of hydrolluoric acid or hydrogen fluoride 13 to the supernatant solution will cause precipitation of alloying element present either as an excess of the make-up addition or as a slightly soluble fluoride, e.g., a rare earth tluoride. Since thorium fluoride is relatively insoluble, the loss of thorium would be negligible if the hydrofluoric acid addition were omitted unless an excess of make-up thorium oxide had been added. There is indicated in the drawing, by broken lines, that the addition of hydrotluoric acid to the reactor is an alternative procedure.

After the acid digestion period, the solidsv14, comprising mainly 4or entirely the precipitated converted lluoride, are separated from the solution by suitable means 15, such as counter-current decantation or filtration, and washed 16 free of soluble magnesium salts 17 with dilute hydrochloric acid, eg., 5 percent HCl, or water. Dilute hydrochloric acid is to be preferred since it prevents peptization of the precipitate. Dilute nitric acid would serve the same purpose but residual *nitratey ion is uridesirable if the product is to be used to make an alloy. Recovered iluoride 18 is dried 19 at 110 to 250" C. depending on lthe desired end use of the dried product 20. If the product must be nearly anhydrous, it is advantageously dried at 200 to 250 C.

Referring now to Figure 2, a combination of steps, ybeginning With the acid digestion in the reactor 11, is shown to illustrate another mode of practicing the invention in which the soluble portion of the fluoride of the alloying element is recovered from the digestion slurry in a different manner. At the end of the digestion period, the precipitatedV fluoride is separated from the supernatant solution 14 by suitable means such as decantation or filtration `15, and washed with dilute hydrochloric acid or water 16. This recovered fluoride v18 is then put through a drier 19 -to obtain a dried product fluoride 20 as before. I 'he combined filtrate and acid washings 17 containing dissolved uoride of the alloying element', soluble magnesium salts and dilute mineral acid is treated with oxalic acid in av precipitation vessel 21 for the purpose of 4precipitating the oxalate of the alloying element. The precipitate in the mixture 23 is separated from it by suitable means 24 such as filtration. The filtrate v25 may be discarded or put through a mineral acid recovery step as desired.. 'Ihe oxalate precipitate 26 is dried and ignited to the 4oxide '28 in a combustion furnace 27. The oxide is then recycled as make-up material 10 which is added to the reactor 11 to maintain stoichiometric proportions between magnesium fluoride and the oxide of the alloying element.

The following two examples are illustrative of the practice of the invention in the recovery of thorium from identical portions of the same calcined, leached saline sludge v prepared as follows: A quantity of saline magnesium sludge formed during the production of magnesium-thorium alloys and containing thorium as the oxide and as entrapped metal pellets was leached with water and calcined for 20 hours'at 600 C. The so treated sludge contained 27.7 percent Th, 31.8-percent Mg and 14.7 percent F. An impure grade of ThOz containing 80.4 percent Th and 1.7 percent Fe203 was used for make-up additions of deficient material for the conversion process.

Example I 256.4 ml. water was transferred to a one-liter threenecked ask fitted with a watercooled condenser, a mechanical stirrerand .a heating mantle. Stirring .was

.tent from r83 to95.5 percent.

assai-s55 started and a 77.8 gmrportionjof the l,calcined, leached also described above, were slurried into the water. The

total T1102 present was .calculated to be 96.6 percent of Digestion of the resulting mixture was carried out at a steady reux rate of 3 to 5 ml. per jminute for 48 hours, the'acid concentration then beingLQA molar. Solids were separatedw'from the supernatantjsolution of the digestion product` iny a centrifuge, then transferred to a fritted glassfBiichner funnel and washed with 30fp`ercent vHN03, then sucked dryron the lilter. 0.7 gin. dissolved Th remained in therfiltrate. After ovenddrying at 120 C. the so washed solid material weighed 48.6 gm. and contained 2.37 gm. Mglzand 32.2 gm. Th representing a thorium yrecovery eiiicieiicy of.' V96 percent. Further oven drying of the recovered .fluoride at 250 C. increased T11F4Y content from 87.7 to 92.5 percent.

`Example 1liV 212.3 m1. Water was transferred to a one-liter threenecked flask iitted with awater cooled condenser, a mechanical stirrer and acheating mantle. Stirring was started anda .77.8 gm.;por'tion of the same calcined, leachedsaline vsludge treated in Example I and described above and a 25.1"gm. p'ortionof ThO2,l also described above, were slurricd into the water.` The system was closed and 187.7,.ml. concentrated HNOS was added slowly through the condenser. Digestion was carried out at a steady reilux' rate `of 3 to 5 ml. per minute for 94.2'hours. The final acid concentration was 1.76 molar. Solids werev separated from Lthe supernatant'solution of the digestion product in arcentrifuge then transferred to a frittedfglass Bchner funnel and washed with 30 percent HNO3, then sucked dry on the ilte'r. The filtrate containedll gm. Th. After oven-drying at 120 C. the so wash'edsolid material weighed 53.5 gm. and contained 1.87 gm. MgF2 and 33.5 gm. Th. Further oven dryingv ofV the solid materialv at 250 C.increased'thel ThF4 con- Recovery of 7.0 gm. Th yfrom the filtrate as the fluoride by addition of hydrofluoric acidi in percent'excess of stoichiometric proportion brings the eciency of thorium recovery to 97 percentv The' -following example of theV conversion reaction performed without the addition of Vmake-up oxide serves as a comparisonwith the practice of this invention as shown above in Examples I and II.v Y f Y 600 ml. watenandfZOO ml. concentrated HNO3 were solid material of the digestion product was separated by filtration ona fritted glass Bchner lfunnel and Washed vwith 30 percent HNOS; then sucked dry on the filter. Thetiltrate contained 0.7",gm. Th'. After oven-drying at 120 C. theffsolidmaterial weighed 36.3 gm. and contained 7.56 gm. ylVIgl-'iz and 20.44 ggm. Th.` The Th content isequivalentto 74.8 percent ThF.' The eiiiciency offthoriu'm recovery is 95 percent. v The following two examples areillus'trativeof lthe change in composition of the insoluble phase as the acid digestion proceeds lduring the practice of the invention in the recovery ofthoriuni.-V They show. that asubstantial-ly pure product except for vweien'content' mayA be' obtainedl byi'usin'g ai large excess` OTh'OZinLth digestonstep.

vA quantityiof saline vmagnesiumA sludge" formed during the production of magnesium-thoriu'malloy's was treated in accordance with the invention. i The sludge` containingr thoriumas the oxide and as entrappedV metal pellets was lea'ched with water and calcinedV for 20 hours Vat 600 C.; The calcined, leached sludge contained 24.6 percent Th.-

23.8per'cent Mg and 9.8 percent F. 74.5'lbslwof this Y material plug 29 lbs. make-up thoriumoxidewas di- 10' gested at 105 C. with 10 gal. concentrated HNO3 Ediluted with 41 gal. water. At the end of the digestion period the acid concentration was 0.4 molar. The insoluble phase'varied in composition during'fthe course V.of the reaction as shown by the data in the accompanying table. The total amount of thorium oxideA present in the calcined, .leached sludge and in added make-up oxide was calculated to be 96 percent inY excess of'the stoichiometric amount.

. Insoluble Phase Digestion Time, Hrs. L

Percent Percent Percent Percent Mg Th glin` ThF4 i K (Cale.) (Calc.) K

17.5 28.1 13.9 11.7 2.82 68.0; v .32 69. 9 o s2 92s Y 'it Example V l 60 lbs. of the same calcined-'andleached saline sludge, described in Example IV, Vplus 31 lbs. make-up Th02 was digested Yat 105 C. in 1Q gal. HNO3` plus 29V gal water.y The total thoriumV oxide present was'calculated to be 135 in excess of the stoichiometric amount. Y At the end ofthe digestion period the acid concentration was 0.14 molar. The insoluble phase changed- 'composition during the course of the digestion as shown by the'data in the accompanying table.

Insoluble Phase In Examples IV and V, 99 percent of the thorium remaining in solutionfis recovered as the 'uoride by precipitation from combined iltratesAv upon the addition of hydrouoric acid in 10 percent excess of stoichio' metric proportions.

g The following are two examples of the recoveryof neodymium, a rare earth 'met-al. Example VIV is illus-v trative of the changeY in 'composition` of the insoluble phase as the acid digestion proceeds during thepractice of ythis invention. As a comparison Example'VII illus;

trates the results obtained when no'make-up neodymiuin l oxide is added during the acid digestion step.

Example VI 1217 gm. of saline magnesium sludge formed during'V the productionv of magnesium-needymium alloys was leachedwitlr2 vliters ofwater. After filtration and dry'- ing at 120 C. the insoluble material weighed 980Y gm. A 500 gm. portion of this leachdand dried material was calcined Vfor 20 hours at`800f C. The calcined materialweighed 398 gm. and contained 10.6 percent Nd, 36.6

percent Mg andv 12.8 percent F.

120 gm. of the abovel calcined and leachedslu'dge was Y combined with 40.5 gm. of neodymiurn oxide, t` pro-Y vide an amount of neodyrnium 18 percent in? excess 'f Percent `Percent Percent Percent' Mg Th MgF2 4" (Calc.) (Calc.)

v Y Insoluble Phase Digestion Timo, Hours Percent Percent Mg Nd 0.5---- 2U. 85 21.95 6.5 8.19 50.5 27. 3.01 G6. 6 51. 1. 84 67. 9 esnilA Aas.

Example VII 79.1 gm. of the same calcined and leached sludge described in Example VI was digested with 250 ml. conc. HC1 plus 150 ml. H2O for 22 hours at 105 C. The final acidrvconcentration was 0.5 molar. The digested mixture was ltered. Theinsoluble phase V.s.o.recovered weighed 15.5 gm. after washing and drying and contained 54.7 percent MgF2 and 45.3 percent neodymium fluoride representing a recovery of 71.1 percent of the neodymium originally present in the calcined sludge. The neodymium not recovered in this step remained in the acid filtrate.

For complete recoveries neodyrnium remaining in the above acid iiltrates, both as the slightly soluble fluoride and as excess make-up oxide brought into solution during acid digestion, must be precipitated and recovered. Neodymium uoride is quantitatively precipitated by adding iluoride, e.g., as hydrofluoric acid, in 150 percent excess of the stoichiometric amount.

Among the advantages of the invention are the absence of costly neutralization steps as well as the elimination of the need for substantial amounts of relatively expensive hydrouoric acid, eicicnt use being made of bound fluorine, already present, for thelconversion of alloying element values to the insoluble fluoride.- Also, the practice' of the process is readily adapted to t the economics of a given situation since the product in substantially pure form may be obtained with as high recoveryA efciency as products of 85 percent purity.

What is claimed is:

1.A process for the recovery of an alloying element of the group consisting of thorium and the rare earth elements from a saline magnesium sludge as generatedy during the production of alloys of magnesium with said 2. vA process as in claim 1 in which the alloying element is thorium and the mineral acid is nitric acid.

f 3. A process as in Vclaim 2 in which the recovered thorium uoride is subjected to drying at temperatures in the range 200 to 250 C.

4. A process as in claim 1 inrwhich thefalloying element is a rare earth metal and the mineral acid is hydrochloric acid.

5. A process for the recovery of an alloying element of the group consisting of thorium and the rare earth metals from a saline magnesium sludge as generated during the production of alloys of magnesium with said alloying element in the presence of a saline tlux, said saline sludge containing magnesium uoride and acidsoluble values of the alloying element, said process comprising leaching the said sludge with an aqueous solvent to remove soluble salts; separating the leached solids from the leaching solution; calcining the separated leached solids; to the calcined leached solids adding material from the class consisting of magnesium uoride and the oxide of the said alloying element in amount suicient to maintain a stoichiometric excess of oxide of the alloying element over magnesium uoride to assure utilization of substantially all of the magnesium uoride in the conversion of lthe said oxide to the iluoride; digesting in a diluted mineral acid selected from the group consisting of nitric, hydrochloric andhydrobromic acid, at an elevated temperature and mixture of delicient material and calcined -product to bring about the said conversion of the oxideof the alloying element to the lluoride; adding the requisite amount of hydrolluoric acid to the supernatant phase of the resulting digestion liquor to precipitate dissolved alloying element as a uoride precipitate;` and recovering the precipitate thereby obtaining substantially pure uoride of the alloying element.

6. A process as in claim 5 in which the alloying element is thorium and the mineral acid is nitric acid.

7. A process as in claim 5 in which the alloying element is a rare earth metal and the mineral acid is hydroalloying element in the presence of a saline ux, said Y saline sludge containing magnesium uoride and acidsoluble values of the alloying element, said process comprising leaching the said sludge with an aqueous solvent to remove soluble salts; separating the leached solids from the resulting leaching solution; calcining the separated leached solids; to the calcined leached solids adding material from the class consisting of magnesium uoride and the oxide of the said alloying element in amount sufficient to maintain stoichiometric proportions between magnesium uoride and the oxide of the alloying element in the calcined leached solids for the conversion of the oxide to the fluoride; digesting the mixture so obtained in a mineral acid of the group consisting of nitric, hydrochloric and hydrobromic acid at an elevated temperature so as to bring about said conversion; recovering and Washing the precipitate from the resulting digestion mixture; and drying the said precipitate at a temperature 'C excess of 100 C., thereby recovering the-fluoride of thealloying element. Y Y

chloric acid. f

8. A process as in claim 5 in which the alloying element is a rare earth metal and the mineral acid is nitric acid.

9. A process for the recovery of an alloying element of the group consisting of thorium and the rare earth metals from a saline magnesium sludge as generated during the production of alloys of magnesium withsaid alloying element in the presence of a saline ux, said saline sludge containingmagnesium fluoride and acidsoluble values of the alloying element, said process comprising leaching the said sludge with an aqueous solvent to remove soluble salts; separating the leached solids from the leaching solution; calcining the separated leached solids; to the calcined leached solids adding material from the class consistingv of magnesium uoride and the oxide of the said alloying element in amount suiiicient to maintain a stoichiometric excess of oxide of the alloying element over magnesium fluoride to assure utilization of substantially all of the magnesium fluoride in the conversion of the said oxide to the uoride; digesting the mixture so obtained in a mineral acid selected from the group consisting of nitric, hydrochloric and hydrobromic acid, at an elevated temperature to bring about the said conversion of the oxide of the alloying element to the uoride; separating precipitated fluoride from the supernatant solution; then recovering dissolved alloying element from the supernatant solution by precipitating the alloying element as the oxalate; separating the precipitated oxalate from the solution; igniting the separated oxalate to the oxide; recycling the so obtained oxide in the process as make-up material; and drying the aforesaid precipitated fluoride at a temperature in excess of C., thereby recovering substantiallypure iluoride of the alloying element.

10. A process as in claim ,9. in which the alloying calcining the separated leached solids; to the calcined Y leached solids adding material from the class consisting of magnesium iuoride and the oxide of the said rare earth metal in amount suicient to maintain stoichiometric proportions between magnesium uoride and the oxide of the rare earth metal in the calcined leached solids for the conversion of the oxide to the uoride; digesting the mixture so obtained in a mineral acid selected from the group consisting of nitric, hydrochloric and hydrobromic acid, at an elevated temperature so as to bring about said conversion; adding the requisite amount of hydrofluoric acid to the supernatant phase of the resulting digestion liquor to precipitate dissolved rare earth metal as additional uoride precipitate; separating the combined precipitate from the supernatant solution; and drying the precipitate at a temperature in excess of 100 C.y t

l 12. A process for the recovery of a rare earth metal from a saline magnesium sludge as generated during the production of alloys of magnesium with said rare earth 30 2,546,933

metal in the presence of a saline flux, said saline sludge containing magnesium fluoride and acid soluble rare earth metal values, said process comprising leaching the said sludge with an aqueous solvent to remove soluble salts;

- separating the leached solids from the leaching solution;

calcining the separated leached solids; to the calcined leached solids adding material from the class consisting of magnesium fluoride and the oxide of the said rare earth metal in amount suicient to maintain stoichiometric proportions between magnesium uoride and the oxide of the rare earth metal in the calcined leached solids for the conversion of the oxide to the fluoride; digesting the mixture so obtained in a mineral acid selected from the group consisting of nitric, hydrochloric and hydrobromic acid, at an elevated temperature so as the solution; igniting the separated oxalate to the oxide;

K ,References Cited in the le of this patent UNITED STATES PATENTS Steahly et al. Mar. 27, 1951 

1. A PROCESS FOR THE RECOVERY OF AN ALLOYING ELEMENT OF THE GROUP CONSISTING OF THORIUM AND THE RARE EARTH ELEMENTS FROM A SALINE MAGNESIUM SLUDGE AS GENERATED DURING THE PRODUCTION OF ALLOYS OF MAGNESIUM WITH SAID ALLOYING ELEMENT IN THE PRESENCE OF A SALINE FLUX, SAID SALINE SLUDGE CONTAINING MAGNESIUM, FLUORIDE AND ACIDSOLUBLE VALUES OF THE ALLOYING ELEMENT, SAID PROCESS COMPRISING LEACHING THE SAID SLUDGE WITH AN AQUEOUS SOLVENT TO REMOVE SOLUBLE SALTS, SEPARATING THE LEACHED SOLIDS FROM THE RESULTING LEACHING SOLUTION, CALCINING THE SEPARATED LEACHED SOLIDS, TO THE CALCINED LEACHED SOLIDS ADDING MATERIAL FROM THE CLASS CONSISTING OF MAGNESIUM FLUORIDE AND THE OXIDE OF THE SAID ALLOYING ELEMENT IN AMOUNT SUFFICIENT TO MAINTAIN STOICHIOMETRIC PROPORTIONS BETWEEN MAGNESIUM FLUORIDE AND THE OXIDE OF THE ALLOWYING ELEMENT IN THE CALCINED LEACHED SOLIDS FOR THE CONVERSION OF 